US5457022A - Silver halide photographic material - Google Patents
Silver halide photographic material Download PDFInfo
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- US5457022A US5457022A US08/262,340 US26234094A US5457022A US 5457022 A US5457022 A US 5457022A US 26234094 A US26234094 A US 26234094A US 5457022 A US5457022 A US 5457022A
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- silver halide
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C1/12—Methine and polymethine dyes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
Definitions
- the present invention relates to a high-sensitivity silver halide photographic material.
- Color sensitization technology is extremely important and is indispensable for producing high-sensitivity photographic materials with excellent color reproducibility.
- a color sensitizer inherently has a function of absorbing light with a long wavelength range which is not substantially absorbed by silver halide photographic emulsions and of transmitting the energy of the absorbed light to the silver halide. Therefore, increasing the amount of light to be captured by a color sensitizer is advantageous for elevating the photographic sensitivity of a photographic material. Accordingly, attempts have heretofore been made to elevate the amount of light to be captured by a color sensitizer by increasing the amount of the color sensitizer to be added to the silver halide emulsion.
- dye desensitization is a phenomenon resulting in desensitization in the light-sensitive range intrinsic to a silver halide substantially free from color absorption by a sensitizing dye. If dye desensitization of a photographic material is great, then the total sensitivity of the photographic material will be low even though the material may be heavily color-sensitized. In other words, decreasing dye desensitization causes a proportional elevation of the sensitivity of the light-absorbing range by a color sensitizer (namely, the color sensitivity of a color sensitizer itself).
- JP-A as used herein means an "unexamined published Japanese patent application”.
- these proposed methods are limited to specific sensitizing dyes and the effects thereof are still unsatisfactory.
- JP-B as used herein means an "examined Japanese patent publication”.
- M-band sensitizing dyes which show a gently-sloping sensitization peak in a relatively long wavelength range, such as dicarbocyanines, tricarbocyanines, rhodacyanines and merocyanines.
- U.S. Pat. No. 3,695,888 discloses combination of a tricarbocyanine and an ascorbic acid to yield infrared sensitization of a photographic material
- British Patent 1,255,084 discloses combination of a particular dye and an ascorbic acid to yield elevation of the minus-blue sensitivity of a photographic material
- British Patent 1,064,193 discloses combination of a particular dye and an ascorbic acid to yield elevation of the sensitivity of a photographic material
- U.S. Pat. No. 3,809,561 discloses combination of a desensitizing nucleus-containing cyanine dye and a supercolor sensitizer such as an ascorbic acid.
- the preceding technology often displays an unsatisfactory sensitizing effect of the dyes used, and even if a high sensitizing effect is attained, it often causes an increase of fog of the photographic material.
- sensitizing dyes having a reduction potential of -1.25 V or more are low in a relative quantum yield of spectral sensitization as described in T. Tani et al., Journal of the Physical Chemistry, vol. 94, page 1298 (1990). It is proposed in the aforesaid The Theory of the Photographic Process, Forth Edition, pages 259-265 (1977) that super-sensitization is conducted by positive hole capture to increase the relative quantum yield of spectral sensitization. However, it is highly demanded to provide more effective supersensitizing agents.
- An object of the present invention is to provide a silver halide photographic material, particularly a spectral-sensitized silver halide photographic material, which has high sensitivity and which does not tend to fog.
- Another object of the present invention is to provide a silver halide photographic material which has high storage stability.
- a silver halide photographic material particularly preferably spectral-sensitized silver halide photographic material, comprising a support having thereon at least one silver halide emulsion layer, wherein at least one layer contains at least one metallocene compound.
- the metallocene is a general term for biscyclopentadienyl metal compounds [described in Iwanami Rikagaku Jiten, the third edition an enlarged edition, page 1335 edited by Bunichi Tamamushi et al., (published by Iwanami Shoten 1986) (written in Japanese)].
- the metallocene compound is selected from the compounds represented by the following formula (I): ##STR1## wherein M represents Fe, Ti, V, Cr, Co, Ni, Ru, Os or Pd; and V 1 , V 2 , V 3 , V 4 , V 5 , V 6 , V 7 , V 8 , V 9 and V 10 are the same or different and each represents a hydrogen atom or a monovalent substituent, provided that two of V 1 , V 2 , V 3 , V 4 , V 5 , V 6 , V 7 , V 8 , V 9 and V 10 may be combined with each other to form a ring; or two or more of the metallocene compounds may be combined together.
- M represents Fe, Ti, V, Cr, Co, Ni, Ru, Os or Pd
- V 1 , V 2 , V 3 , V 4 , V 5 , V 6 , V 7 , V 8 , V 9 and V 10 are the same or different and each represents a hydrogen atom or
- the compounds where M is Fe are more preferred and are called ferrocene compounds.
- V 1 , V 2 , V 3 , V 4 , V 5 , V 6 , V 7 , V 8 , V 9 and V 10 are the same or different and each represents a hydrogen atom or a monovalent substituent.
- Examples of preferred substituents represented by V 1 to V 10 include an unsubstituted alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, cyclopentyl, cyclopropyl, cyclohexyl); a substituted alkyl group (when the substituent attaching to the alkyl group is referred to as V, examples of the substituent represented by V include, but are not limited to, a carboxyl group, a sulfo group, a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a hydroxyl group, an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), an ary
- the examples of preferred substituent represented by V include a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2-cyanoethyl, 2-chloroethyl, 2-bromoethyl, 2-hydroxyethyl, 3-hydroxypropyl, hydroxymethyl, 2-hydroxyethyl, 4-hydroxybutyl, 2,4-dihydroxybutyl, 2-methoxyethyl, 2-ethoxyethyl, methoxymethyl, 2-ethoxycarbonylethyl, methoxycarbonylmethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-
- the substituents represented by V 1 to V 10 have more preferably from 1 to 18 carbon atoms.
- V 1 to V 10 may be combined with each other to form a ring.
- the ring may be any of an aliphatic ring and an aromatic ring.
- the ring amy be substituted by one or more of the substituents represented by V.
- the metallocene compounds used in the present invention can be synthesized by referring to the method described in D. E. Bublitz et al., Organic Reactions, vol. 17, pp 1-154 (1969).
- metallocene compounds and the ferrocene compounds are conveniently expressed by formula (I) in the present invention. However, these compounds can be expressed by other formulae and refer to the same compounds, though these compounds are expressed by different formulae.
- the effect obtained by the metallocene compounds of the present invention is particularly remarkable when the metallocene compounds are contained in the silver halide photographic materials spectral-sensitized by spectral sensitizing dyes.
- the spectral sensitizing dyes which can be used in the present invention include any of conventional dyes such as cyanine dyes, merocyanine dyes, rhodacyanine dyes, oxonol dyes, hemicyanine dyes, benzylidene dyes and xanthene dyes. Examples of these dyes are described in T. H. James, The Theory of the Photographic Process, the third edition, pp. 198-228 (1966) (Macmillan Co.).
- sensitizing dyes having an oxidation potential of 0.95 (V VS SCE) or less are preferred (the term “SCE” as used herein means a "saturated calomel electrode”). It is known that these dyes generally cause greatly dye desensitization.
- sensitizing dyes having a reduction potential of -1.3 (V VS SCE) or more are preferred. It is known that these dyes are generally low in the relative quantum yield of spectral sensitization.
- oxidation and reduction potentials were carried out by a phase discrimination second higher frequency alternating current polargraphy. The detail of the measurement is described below.
- Acetonitrile (spectral grade) dried in 4A-1/16 molecular sieves was used as the solvent.
- n-Tetrapropylammonium perchlorate (special reagent for a polargraphy) was used as the supporting electrolyte.
- a sample solution was prepared by dissolving from 10 -3 to 10 -5 mol of a sensitizing dye per liter in acetonitrile containing 0.1M supporting electrolyte.
- the sample solution was deoxidized for at least 15 minutes by using ultra-high-purity argon gas (99.999%) passed through a highly alkaline aqueous solution of pyrogallol and a tube packed with calcium chloride.
- a rotating platinum electrode was used as the working electrode in the measurement of oxidation potential, and a dropping mercury electrode was used as the working electrode in the measurement of reduction potential.
- Saturated calomel electrode (SCE) was used as a reference electrode, and platinum was used as an opposite electrode.
- the reference electrode was connected with the sample solution by means of a Luggin tube filled with acetonitrile containing 0.1M supporting electrolyte, and Vycor glass was used for a liquid junction part.
- the top of the Luggin tube was from 5 to 8 mm away from the top of the rotating platinum electrode, and the measurement was carried out at 25° C.
- the above measurement of oxidation and reduction potentials by the phase discrimination second higher frequency alternating current voltmmetry is described in Journal of Imaging Science, vol. 30, pp. 27-35 (1986).
- the dye (XIV-9) described hereinafter had an oxidation potential of 0.915 (V VS SCE) and a reduction potential of -1.22 (V VS SCE).
- Sensitizing dyes represented by the following formulae (XI), (XII) and (XIII) can be particularly preferably used: ##STR31##
- Z 11 , Z 12 , Z 13 , Z 14 , Z 15 and Z 16 are the same or different each represents an atomic group necessary for forming a five-membered or six-membered nitrogen-containing heterocyclic ring.
- D and D' are the same or different and each represents an atomic group necessary for forming a non-cyclic or cyclic acid nucleus.
- R 11 , R 12 , R 13 , R 14 and R 16 are the same or different and each represents a substituted or unsubstituted alkyl group.
- R 15 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.
- L 11 , L 12 , L 13 , L 14 , L 15 , L 16 , L 17 , L 18 , L 19 , L 20 , L 21 , L 22 , L 23 , L 24 , L 25 , L 26 , L 27 , L 28 , L 29 and L 30 are the same or different and each represents a substituted or unsubstituted methine group.
- M 11 , M 12 and M 13 are the same or different and each represents a counter ion for neutralizing charge; m 11 , m 12 and m 13 are the same or different and each represents a number of 0 or more necessary for neutralizing the molecular charge; n 11 , n 13 , n 14 , n 16 and n 19 are the same or different and each represents 0 or 1; and n 12 , n 15 , n 17 and n 18 are the same or different and each represents an integer of 0 or more.
- the sensitizing dyes represented by formula (XI) called cyanine dyes are more preferred.
- R 11 , R 12 , R 13 , R 14 and R 16 are each an unsubstituted alkyl group having from 1 to 18 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl) or a substituted alkyl group ⁇ for example, an alkyl group having from 1 to 18 carbon atoms substituted by one or more of substituents such as a carboxyl group, a sulfo group, a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine), a hydroxyl group, an alkoxycarbonyl group having from 2 to 8 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group having from 1 to 8 carbon atoms (
- R 11 , R 12 , R 13 , R 14 and R 16 are each an unsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl), a carboxyalkyl group (e.g., 2-carboxyethyl, carboxymethyl), a sulfoalkyl group (e.g., 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl) or a methanesulfonylcarbamoylmethyl group.
- alkyl group e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl
- a carboxyalkyl group e.g., 2-carboxyethyl, carboxy
- M 11 m 11 , M 12 m 12 and M 13 m 13 are each included in the formulae to show the presence or absence of a cation or an anion when it is necessary for neutralizing the ionic charge of the dye. Whether a certain dye is cationic, anionic or neutral depends on the auxochrome and the substituents in the dye.
- Typical examples of the cation include inorganic or organic ammonium ions (e.g., ammonium ion, tetraalkyl ammonium ion, pyridinium ion), an alkali metal ion (e.g., sodium ion, potassium ion) and an alkaline earth metal ion (e.g., calcium ion).
- the anion may be any of an inorganic ion and an organic ion.
- the anion include a halide ion (e.g., fluoride ion, chloride ion, bromide ion, iodide ion), a substituted arylsulfonate ion (e.g., p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), an aryldisulfonate ion (e.g., 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), an alkylsulfate ion (e.g., methylsulfate ion, ethylsulfate ion), a sulfate ion, a thiocyanate ion, a
- an ionic polymer or other dyes having an opposite charge to that of the sensitizing dye may be used as a counter ion for neutralizing charge.
- a metal complex ion e.g., bisbenzene-1,2-dithiolatonickel (III)
- III bisbenzene-1,2-dithiolatonickel
- Preferred ions are an ammonium ion, an iodide ion and a p-toluenesulfonate ion.
- n 11 , m 12 and m 13 are each 0, 1 or 2.
- Examples of the nucleus formed by Z 11 , Z 12 , Z 13 , Z 14 or Z 16 include a thiazole nucleus [for example, a thiazole nucleus (e.g., thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole), a benzothiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 6-methylthiobenzothiazole, 5-ethoxybenz
- Preferred examples of the nucleus formed by Z 11 , Z 12 , Z 13 , Z 14 or Z 16 include a benzthiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus and a 4-quinoline nucleus.
- D and D' each represents an atomic group necessary for forming an acid nucleus and may be in any form of the acid nuclei of conventional merocyanine dyes.
- the term "acid nucleus" as used herein refers to the nucleus defined, for example, by T .H. James, The Theory of the Photographic Process, the fourth edition, page 198 (Macmillan Co. 1977).
- substituent groups which participate in the resonance of D include a carbonyl group, a cyano group, a sulfonyl group and a phenyl group.
- D' is the residual moiety of the atomic group necessary for forming the acid nucleus.
- the terminal of the methine bond is such a group as derived from a malononitrile group, an alkanesulfonylacetonitrile group, a cyanomethylbenzofuranylketone group or a cyanomethylphenylketone group.
- the acid nucleus formed by D and D' is a cyclic nucleus
- a five-membered or six-membered heterocyclic ring comprising carbon, nitrogen or chalcogen (typically, oxygen, sulfur, selenium, tellurium) atoms is formed.
- Preferred examples of the acid nucleus include 2-pyrazoline-5-one, pyrazolidine-3,5-dione, imidazoline-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminoxazolidine-4-one, 2-oxazoline-5-one, 2-thioxazolidine-2,4-dione, isoxazoline-5-one, 2-thiazoline-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, thiophene-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, indazoline-3-one, 2-oxoindazolium, 3-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo[3,2-a
- nuclei of 3-alkylrhodanine, 3-alkyl-2-thioxazolidine-2,4-dione and 3-alkyl-2-thiohydantoin are more preferred.
- R 15 and the substituents attached to the nitrogen atom in the acid nucleus each represents a hydrogen atom, an alkyl group having from 1 to 18 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), an aryl group having from 6 to 18 carbon atoms (e.g., phenyl, 2-naphthyl, 1-naphthyl) or a heterocyclic group having from 1 to 18 carbon atoms (e.g., 2-pyridyl, 2-thiazolyl, 2-furyl).
- an alkyl group having from 1 to 18 carbon atoms e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dode
- substituents include a carboxyl group, a sulfo group, a cyano group, a nitro group, a halogen atom (e.g., fluorine, chlorine, iodine, bromine), a hydroxyl group, an alkoxy group having from 1 to 8 carbon atoms (e.g., methoxy, ethoxy, benzyloxy, phenethyl), an aryloxy group having from 6 to 15 carbon atoms (e.g., phenoxy), an acyloxy group having from 2 to 8 carbon atoms (e.g., acetyloxy), an alkoxycarbonyl group having from 2 to 8 carbon atoms, an acyl group having from 2 to 8 carbon atoms, a sulfamoyl group, a carbamoyl group, an alkanesulfonylaminocarbonyl group having from 2 to 8 carbon atoms (e.
- an unsubstituted alkyl group e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl
- a carboxyalkyl group e.g., carboxymethyl, 2-carboxyethyl
- a sulfoalkyl group e.g., 2-sulfoethyl
- the five-membered or six-membered nitrogen-containing heterocyclic ring formed by Z 15 is a ring formed by removing oxo group or thioxo group at an appropriate position from a heterocyclic ring formed by D and D', preferably a ring formed by removing a thioxo group from a rhodanine nucleus.
- L 11 , L 12 , L 13 , L 14 , L 15 , L 16 , L 17 , L 18 , L 19 , L 20 , L 21 , L 22 , L 23 , L 24 , L 25 , L 26 , L 27 , L 28 , L 29 and L 30 each represents a methine group or a substituted methine group [for example, a methine group substituted by one or more of a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted aryl group (e.g., phenyl, o-carboxyphenyl), a halogen atom (e.g., chlorine, bromine), an alkoxy group (e.g., methoxy, ethoxy), an amino group (e.g., N,N-diphenylamino, N-methyl-N-phenylamin
- L 11 , L 12 , L 16 , L 17 , L 18 , L 19 , L 22 , L 23 , L 29 and L 30 are each an unsubstituted methine group.
- h 12 is 0, 1, 2 or 3.
- Methine dyes such as monomethine, trimethine, pentamethine and heptamethine dyes can be formed by L 13 , L 14 and L 15 .
- n 12 is 2 or more, an L 13 -L 14 unit is repeated, but the repeating units may be different.
- L 13 , L 14 and L 15 include the following groups: ##STR32##
- n 15 is 0, 1, 2 or 3.
- Methine dyes such as zeromethine, dimethine, tetramethine and hexamethine dyes can be formed by L 20 and L 21 .
- n 15 is 2 or more, an L 20 -L 21 unit is repeated, and the repeating units may be different.
- L 20 and L 21 include the following groups: ##STR33##
- n17 is 0, 1, 2 or 3.
- Methine dyes such as zeromethine, dimethine, tetramethine and hexamethine dyes can be formed by L24 and L 25 .
- n 17 is 2 or more, an L 24 -L 25 unit is repeated, and the repeating units may be different.
- L 24 and L 25 are the same as those of L 20 and L 21 .
- h 18 is 0, 1, 2 or 3.
- Methine dyes such as monomethine, trimethine, pentamethine and heptamethine dyes can be formed by L 26 , L 27 and L 28 .
- n 18 is 2 or more, an L 26 -L 27 unit is repeated, and the repeating units may be different.
- L 26 , L 27 and L 28 include the following groups: ##STR34##
- the compound represented by formula (XI) is more preferably represented by the compound represented by the following formula (XIV): ##STR35## wherein Z 17 and Z 18 are the same or different and each represents a sulfur atom or a selenium atom.
- R 17 and R 18 are the same or different and each represents a substituted or unsubstituted alkyl group.
- R 19 , V 11 , V 12 , V 13 , V 14 , V 15 , V 16 , V 17 and V 18 are the same or different and each represents a hydrogen atom or a monovalent substituent.
- M 14 represents a counter ion fro neutralizing charge; and m 14 represents a number of 0 or more necessary for neutralizing the molecular charge.
- R 17 an R 18 have the same meaning as R 11 , R 12 , R 13 , R 14 and R 16 .
- Examples of te substituent represented by R 19 , V 11 , V 12 , V 13 , V 14 , V 15 , V 16 , V 17 or V 18 include, but are not limited to, those already described above in the definition of the substituent group represented by V 1 to V 10 .
- Adjacent two of V 11 , V 12 , V 13 , V 14 , V 15 , V 16 , V 17 and V 18 may be combined with each other to form a condensed ring.
- condensed ring examples include those comprising a benzene ring and a heterocyclic ring (e.g., pyrrole, thiophene, furan, pyridine, imidazole, triazole, thiazole).
- a heterocyclic ring e.g., pyrrole, thiophene, furan, pyridine, imidazole, triazole, thiazole.
- R 19 is preferably a methyl group, an ethyl group, a propyl group or a cyclopropyl group, and more preferably an ethyl group.
- V 11 , V 12 , V 14 , V 15 , V 16 and V 18 are each a hydrogen atom.
- V 13 and V 17 are each a chlorine atom, a methyl group, a methoxy group, a phenyl group or a carboxyl group.
- V 13 and V 14 or V 17 and V 18 are combined together to form a benzene ring.
- M 14 m 14 has the same meaning as M 11 m 11 , M 12 m 12 and M 13 m 13 .
- sensitizing dyes which can be used in the present invention include, but are not limited to, the following compounds.
- the sensitizing dyes are described in order of higher conception, and more preferred sensitizing dyes included in lower conception are excluded.
- the sensitizing dyes used in the present invention can be synthesized by the methods described in F. M. Hamer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds (John & Sons New York London 1964), D. M. Sturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry-, chapter 18, paragraph 14, pp. 482-515 (John Wiley & Sons New York London 1977), and Rodd's Chemistry of Carbon Compounds, 2nd ed., vol. IV, part B (1977), chapter 15, pp. 369-422 and 2nd ed., vol. IV, part B (1985), chapter 15, pp. 267-296 (Elsvier Science Publishing Company Inc., New York).
- the metallocene compounds of the present invention and the sensitizing dyes used in the present invention may be directly dispersed in the silver halide emulsions used in the present invention.
- the metallocene compounds and the sensitizing dyes may be dissolved in a solvent such as water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol or N,N-dimethylformamide alone or a mixture thereof, and the resulting solution may be added to the emulsions.
- a solvent such as water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-
- ultrasonic wave can be used to dissolve the dye and the metallocene compound represented by formula (I).
- the sensitizing dyes used in the present invention and the metallocene compounds may be added to the emulsions during the preparation of the emulsions at any stage conventionally considered to be advantageous.
- they may be added during the formation of silver halide grains and/or before desalting, or during desalting and/or before chemical sensitization after desalting as described in U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756 and 4,225,666, JP-A-58-184142 and JP-A-60-196749. They may be added immediately before or during chemical ripening or at any stage before coating after chemical ripening as described in JP-A-58-113920.
- the same compound alone or a combination of compounds having different structures may be divided into two or more portions and added. For example, a part thereof is added during the formation of the grains, and the remainder is added during or after chemical ripening. A part thereof is added before chemical ripening, and the remainder is added after completion of chemical ripening.
- the types of compounds to be divided or the combinations of compounds may be changed and added.
- the amounts of the sensitizing dyes to be added vary depending on the form and size of the silver halide grains, but are preferably used in an amount of from 4 ⁇ 10 -8 to 8 ⁇ 10 -2 mol per mol of silver halide.
- the metallocene compounds of the present invention may be added before or after the addition of the sensitizing dyes and are used in an amount of preferably from 1 ⁇ 10 -6 to 5 ⁇ 10 -5 mol, more preferably from 1 ⁇ 10 -5 to 2 ⁇ 10 -2 mol, and most preferably from 1 ⁇ 10 -4 to 1.6 ⁇ 10 -2 mol, per mol of silver halide in the silver halide emulsion.
- the ratio (by mol) of the sensitizing dye to the metallocene compound is not particularly limited. However, the ratio of the sensitizing dye/the metallocene compound is preferably from 100/1 to 1/1000, more preferably from 10/1 to 1/100.
- the silver halide used in the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide and silver iodobromide.
- the silver halide emulsions used in the present invention may contain one kind of silver halide grains or a mixture of two or more kinds of silver halide grains.
- Silver halide grains may be different in phase between the interior of the grain and the surface layer thereof.
- the silver halide grains may have a polyphase structure having a joint structure.
- the silver halide grains may have localized phases on the surface of the grain.
- the silver halide grains may comprise a uniform phase throughout the entire grain or may be in the mixed form of a uniform phase and other phases.
- the silver halide grains used in the present invention may be a monodisperse type or a polydisperse type, and may have a regular crystal form such as a cubic, octahedral or tetradecahedral form, an irregular crystal form or a composite form of these crystal forms.
- tabular emulsions comprising grains having such a grain size distribution that AgX grains having an aspect ratio (a ratio of the diameter of the grain in terms of the diameter of the corresponding circle to the thickness of the grain) of 3 or more account for 50% or more of the entire projected areas of the entire grains. An aspect ratio of from 5 to 8 is more preferred.
- Emulsions may comprise a mixture of grains having various crystal forms.
- the emulsions may be a surface latent image type wherein a latent image is predominantly formed on the surface of the grain or an internal latent image type wherein a latent image is predominantly formed in the interior of the grain.
- the photographic emulsions used in the present invention can be prepared by the methods described in the literature such as P. Glafkides, Chemie et Physique Photographique (Paul Montel 1967), G. F. Daffin, Photographic Emulsion Chemistry (Focal Press 1966), V. L. Zelikman et al., Making and Coating Photographic Emulsion (Focal Press 1964), F. H. Claes et al., The Journal of Photographic Science, (21) pages 39 to 50 (1973) and (21) pages 85-92 (1973) and in the patent specifications of JP-B-55-42737, U.S. Pat. Nos.
- any of the acid process, the neutral process and the ammonia process can be used.
- a soluble silver salt and a soluble halide can be reacted by the single jet process, the double jet process or a combination thereof.
- a method wherein grains are formed in the presence of an excess of silver (called a reverse mixing method) can be used.
- a type of the double jet process a method wherein the pAg in a liquid phase in which silver halide is formed is kept constant, that is, the controlled double jet process can also be used. According to this process, a silver halide emulsion wherein the grain form is regular and the grain size is nearly uniform can be obtained.
- the present invention can use emulsions prepared by a conversion method including the step of converting silver halide already formed during the course of the formation of silver halide grains and emulsions prepared by a conversion method including the step of converting silver halide grains after completion of the formation of the silver halide grains.
- Solvents for silver halide may be used during the preparation of the silver halide grains used in the present invention.
- the solvents for silver halide which are often used include thioether compounds (e.g., those described in U.S. Pat. Nos. 3,271,157, 3,574,628, 3,704,130 and 4,276,347), thione compounds and thiourea compounds (e.g., those described in JP-A-53-144319, JP-A-53-82408, JP-A-55-77737) and amine compounds (e.g., those described in JP-A-54-100717). Further, ammonia can be used in an amount which does not provide any adverse effect.
- the addition rates of the silver salt solution e.g., an aqueous solution of silver nitrate
- the halide solution e.g., an aqueous solution of sodium chloride
- the amounts and concentrations thereof are increased with time to expedite the growth of the grains during the preparation of the silver halide grains.
- the methods are described in, for example, British Patent 1,335,925, U.S. Pat. Nos. 3,672,900, 3,650,757 and 4,242,445, JP-A-55-142329, JP-A-55-158124, JP-A-55-113927, JP-A-58-113928, JP-A-58-111934 and JP-A-58-111936.
- a cadmium salt, a zinc salt, a potassium salt, a rhenium salt, a ruthenium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt or a complex salt thereof may be allowed to coexist during the course of the formation of the silver halide grains or during the physical ripening thereof.
- a rhenium salt, an iridium salt, a rhodium salt or an iron salt is preferred.
- the amounts of these salts to be added may be arbitrarily determined.
- the iridium salt e.g., Na 3 IrCl 6 , Na 2 IrCl 6 , Na 3 Ir(CN) 6
- the rhodium salt e.g., RhCl 3 , K 3 Rh(CN) 6
- RhCl 3 , K 3 Rh(CN) 6 is used in an amount of preferably from 1 ⁇ 10 -8 to 1 ⁇ 10 -5 mol per mol of silver.
- the silver halide emulsions used in the present invention may be used without chemical sensitization. If desired, the silver halide emulsions may be chemical-sensitized.
- Examples of chemical sensitization methods include gold sensitization method using gold compounds (described in, for example, U.S. Pat. Nos. 2,448,060 and 3,320,069), sensitization method using metal such as iridium, platinum, rhodium or palladium (described in, for example, U.S. Pat. Nos. 2,448,060, 2,566,246 and 2,566,263), sulfur sensitization method using sulfur-containing compounds (described in, for example, U.S. Pat. No. 2,222,264), selenium sensitization method using selenium compounds and reduction sensitization method using tin salts, thiourea dioxide or polyamides (described in, for example, U.S. Pat. Nos. 2,487,850, 2,518,698 and 2,521,925). These sensitization methods may be used either alone or in a combination of two or more of them.
- the silver halide emulsions used in the present invention are subjected to gold sensitization, sulfur sensitization or a combination thereof.
- Gold sensitizing agents and sulfur sensitizing agents are used in an amount of preferably from 1 ⁇ 10 -7 to 1 ⁇ 10 -2 mol, more preferably 5 ⁇ 10 -6 to 1 ⁇ 10 -3 mol, per mol of silver.
- the gold sensitizing agent and the sulfur sensitizing agent are used in a ratio by mol of preferably from 1:3 to 3:1, more preferably from 1:2 to 2:1.
- chemical sensitization is carried out at a temperature of from 30° to 90° C.
- the pH thereof is from 4.5 to 9.0, preferably from 5.0 to 7.0.
- the time of chemical sensitization varies depending on the temperature, the pH and the types and amounts of the chemical sensitizing agents used, and may be over a period of several minutes to several hours, but is usually from 10 to 200 minutes.
- the sensitizing dyes are used together with water-soluble iodides such as typically potassium iodide, water-soluble bromides such as typically potassium bromide and water-soluble thiocyanates such as typically potassium thiocyanate to enhance adsorptivity to silver halide or the formation of J-aggregate or to obtain more higher spectral sensitivity.
- water-soluble iodides such as typically potassium iodide
- bromides such as typically potassium bromide
- water-soluble thiocyanates such as typically potassium thiocyanate
- High silver chloride emulsions having a silver chloride content of 50 mol % or more are preferred to conduct ultra-high rapid processing where development time is 30 seconds or less.
- concentration of iodide ion including the above-described water-soluble iodides is 0.05 mol % or less because the iodide ion possesses a high development inhibiting effect.
- High silver chloride emulsions having a silver chloride content of 80 mol % or more are more preferred to prepare ultra-high rapid processable silver halide photographic materials.
- the use of the sensitizing dyes together with the water-soluble bromides and/or the water-soluble thiocyanates is preferred as described above because the formation of J-aggregate can be enhanced and higher spectral sensitivity can be obtained.
- the amounts of these compounds to be added are preferably from 0.03 to 3 mol %, particularly preferably from 0.08 to 1 mol %, per mol of silver.
- High silver chloride grains having a silver chloride content of 80 mol % or more have such a characteristic that when the grains are spectral-sensitized to infrared region, high sensitivity can be obtained, and a latent image having excellent stability can be obtained.
- High silver chloride grains having localized phases described in JP-A-2-248945 are more preferred. It is preferred that the localized phases have a silver bromide content of 15 mol % or more as described in the above patent specification. A silver bromide content of from 20 to 60 mol % is more preferred. It is most preferred that the silver bromide content is from 30 to 50 mol %, and the remainder is silver chloride.
- the localized phases may exist on the surface of the grain or in the interior thereof, or may be distributed so that a portion of the localized phases exists in the interior of the grain, a portion thereof exists on the surface thereof, and a portion thereof exists in the subsurface thereof.
- the localized phases may exist in a laminar structure so that the silver halide grain is surrounded with the localized phases in the interior of the grain or on the surface thereof.
- the localized phases may exist in a discontinuous independent form. In a preferred embodiment of the arrangement of the localized phase having a higher silver bromide content than that of the circumference, the localized phase having a silver bromide content of more than 15 mol % is formed on the surface of the silver halide grain by epitaxial growth.
- the silver bromide content of the localized phase can be analyzed by X-ray diffractometry (e.g., described in New Experimental Chemical Lecture 6, “Structural Analysis", edited by Chemical Society of Japan, published by Maruzen, Japan) or XPS method (e.g., Surface Analysis, IPA, Application of Auger Electron Photoelectron Spectroscopy, published by Kodan-sha, Japan).
- the localized phases are preferably from 0.1 to 20%, more preferably 0.5 to 7%, of silver based on the total amount of silver in the silver halide grain.
- the interface between the localized phase having a high silver bromide content and other phase may be a clear phase boundary or may have a short transition zone where the halogen composition is gradually changed.
- the localized phase having a high silver bromide content can be formed by various methods.
- the localized phases can be formed by reacting a soluble silver salt with a soluble halide according to the single jet process or the double jet process or by a conversion method including a stage where an already formed silver halide is converted to silver halide having a smaller solubility product.
- the localized phases can be formed by adding fine silver bromide grains to silver halide grains to recrystallize the fine silver bromide grains on the surfaces of the silver halide grains.
- the silver halide emulsions prepared according to the present invention can be applied to any of color photographic materials and black and white photographic materials.
- color photographic materials examples include color paper, color films for photographing and reversal color films.
- black and white photographic materials examples include X-ray films, general-purpose films for photographing and films for printing photographic materials.
- Additives described in Research Disclosure vol. 176, No. 17643 (RD 17643) and ibid. vol. 187, No. 18716 (RD 18716) can be applied to the emulsions of the photographic materials used in the present invention without particular limitation.
- Dyes other than sensitizing dye suitable for use in the photographic material of the present invention will be described in detail below.
- the photographic material of the present invention may contain colloidal silver and other dyes for the purpose of anti-irradiation and anti-halation, and especially for separation of the spectral sensitivity distribution of each light-sensitive layer and for ensuring safety to a safelight.
- dyes include, for example, oxonole dyes having pyrazolone nuclei, barbituric nuclei or barbituric acid nuclei, such as those described in U.S. Pat. Nos.
- arylidene dyes such as those described in U.S. Pat. Nos. 2,538,009, 2,688,541 and 2,538,008, British Patents 584,609 and 1,210,252, JP-A-50-40625, JP-A-51-3623, JP-A-51-10927, JP-A-54-118247, JP-B-48-3286 and JP-B-59-37303; styryl dyes such as those described in JP-B-28-3082, JP-B-44-16594, and JP-B-59-28898; triarylmethane dyes such as those described in British Patents 446,538, and 1,335,422, and JP-A-59-228250; merocyanine dyes such as those described in British Patents 1,075,653, 1,153,341, 1,284,730, 1,475,228 and 1,542,807; and cyanine dyes such as those described in U.S. Pat. No
- ballast group may be introduced into the dyes so as to make them non-diffusive.
- a hydrophilic polymer charged oppositely to the dissociated anion dye may be incorporated into a layer along with the dye as a mordant, whereby the dye is localized and fixed in the particular layer due to the interaction of the polymer and the dye molecule, as described in U.S. Pat. Nos. 2,548,564, 4,124,386 and 3,625,694.
- a water-insoluble solid dye may be used for coloring a particular layer, as so described in JP-A-56-12639, JP-A-55-155350, JP-A-55-155351, JP-A-63-278838, JP-A-63-197943, and European Patent 15,601.
- Fine grains of a metal salt to which dyes have been adsorbed may be used for coloring a particular layer, as described in U.S. Pat. Nos. 2,719,088, 2,496,841 and 2,496,842, and JP-A-60-45237.
- the photographic material of the present invention may contain an antifoggant or stabilizer selected from, for example, azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles); mercapto compounds (e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines); thioketo compounds (e.g., oxazolinethiones); azaindenes (e.g., triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)te
- the photographic material of the present invention may contain color couplers, preferably non-diffusive couplers having a hydrophobic group called a ballast group in the molecule or polymerized couplers.
- the couplers may be either 4-equivalent or 2-equivalent with respect to silver ions.
- the photographic material of the present invention may also contain colored couplers having a color-correcting effect, or couplers capable of releasing a development inhibitor during development of the photographic material (so-called DIR couplers).
- the photographic material may also contain colorless DIR coupling compounds capable of producing a colorless product by a coupling reaction and releasing a development inhibitor.
- couplers for use in the present invention are described in JP-A-62-215272, from page 91, right top column, line 4 to page 121, left top column, line 6; and JP-A-2-33144, from page 3, right top column, line 14 to page 18, left top column, last line, and from page 30, right top column, line 6 to page 35, right bottom column, line 11.
- suitable magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylchroman couplers, and open-chain acylacetonitrile couplers;
- suitable yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides); and suitable cyan couplers include naphthol couplers and phenol couplers.
- Preferred cyan couplers include phenol couplers having an ethyl group at the meta-position of the phenol nucleus, 2,5-diacylamino-substitued phenol couplers, phenol couplers having a phenylureido group at the 2-position and having an acylamino group at the 5-position, and naphthol couplers having a sulfonamido or amido group at the 5-position of the naphthol nucleus, such as those described in U.S. Pat. Nos. 3,772,002, 2,772,162, 3,758,308, 4,126,396, 4,334,011, 4,327,173, 3,446,622, 4,333,999, 4,451,559 and 4,427,767, as they form fast images.
- Couplers Two or more different kinds of the above-mentioned couplers may be incorporated into one and the same layer, or one and the same compound of the couplers may be added to two or more layers, for the purpose of satisfying the intended characteristics of the photographic material of the present invention.
- the photographic material of the present invention may contain an anti-fading agent selected from, for example, hindered phenols such as hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols and hisphenols; and gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives of them formed by silylating or alkylating the phenolic hydroxyl group of the compounds.
- metal complexes such as bis(salicylaldoximato)nickel complexes and bis(N,N-dialkyldithiocarbamato)nickel complexes may also be used as an anti-fading agent.
- any known method and any known processing solution may be employed.
- the processing temperature may be selected generally from the range between 18° C. and 50° C. However, it may be lower than 18° C. or higher than 50° C.
- black-and-white development for forming a silver image or color development for forming a color image may be employed.
- any known developing agent such as dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone) and aminophenols (e.g., N-methyl-p-aminophenol) may be employed singly or in combinations of them.
- dihydroxybenzenes e.g., hydroquinone
- 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone
- aminophenols e.g., N-methyl-p-aminophenol
- the color developer for the latter color development is generally an alkaline aqueous solution containing a color developing agent.
- the color developing agent in it may be a known primary aromatic amine developing agent, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N- ⁇ -methoxyethylaniline).
- phenylenediamines e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-
- the developer may additionally contain a pH buffer such as alkali metal sulfites, carbonates, borates or phosphates, as well as a development inhibitor or anti-foggant such as bromides, iodides or organic antifoggants.
- a pH buffer such as alkali metal sulfites, carbonates, borates or phosphates
- a development inhibitor or anti-foggant such as bromides, iodides or organic antifoggants.
- it may also contain a water softener; a preservative such as hydroxylamine; an organic solvent such as benzyl alcohol or diethylene glycol; a development accelerator such as polyethylene glycol, quaternary ammonium salts or amines; a dye forming coupler; a competing coupler; a foggant such as sodium boronhydride; a developing aid such as 1-phenyl-3-pyrazolidone; a thickener; a polycarboxylic acid chelating agent such as those described in U.S. Pat. No. 4,083,723; and an antioxidant such as those described in German Patent OLS No. 2,622,950.
- a water softener such as hydroxylamine
- an organic solvent such as benzyl alcohol or diethylene glycol
- a development accelerator such as polyethylene glycol, quaternary ammonium salts or amines
- a dye forming coupler such as sodium boronhydride
- a competing coupler such as 1-phenyl-3-
- the color photographic material After being color-developed, the color photographic material is generally bleached. Bleaching of the material may be carried out simultaneously with or separately from fixation. Suitable bleaching agents to be used for bleaching the material include, for example, compounds of polyvalent metals such as iron(III), cobalt(III), chromium(VI) and copper(II), as well as peracids, quinones and nitroso compounds.
- bleaching agents include ferricyanides; bichromates; organic complexes of iron(III) or cobalt(III), such as complexes with aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanol-tetraacetic acid) or with organic acids (e.g., citric acid, tartaric acid, malic acid); persulfates; permanganates; and nitrosophenols.
- aminopolycarboxylic acids e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanol-tetraacetic acid
- organic acids e.g., citric acid, tartaric acid, malic acid
- persulfates e.g., citric acid, tartaric acid, malic acid
- persulfates e.
- the bleaching solution or bleach-fixing solution to be used for processing the photographic material of the present invention may contain various additives, for example, a bleaching accelerator such as those described in U.S. Pat. Nos. 3,042,520 and 3,241,966, JP-B-45-8506, and JP-B-45-8836; and a thiol compound such as those described in JP-A-53-65732.
- a bleaching accelerator such as those described in U.S. Pat. Nos. 3,042,520 and 3,241,966, JP-B-45-8506, and JP-B-45-8836
- a thiol compound such as those described in JP-A-53-65732.
- the support of the photographic material of the present invention may be any ordinary transparent film support such as a cellulose nitrate film or polyethylene terephthalate film support, or a reflective support, which is used in forming ordinary photographic materials.
- the "reflective support” of the photographic material of the present invention is one which elevates the reflectivity of the support itself to make the color image formed in the silver halide emulsion layer clear and sharp.
- Reflective supports of this kind include a support coated with a hydrophobic resin containing a dispersion of a photo-reflective substance, such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate, so as to elevate the reflectivity of the support to light within the visible ray wavelength range, and a support made of a hydrophobic resin containing a dispersion of such a photo-reflective substance.
- Suitable reflective supports include a baryta paper, a polyethylene-coated paper, a polypropylene synthetic paper, and a transparent support coated with a reflective layer thereon or containing a reflective substance therein.
- Suitable transparent supports include, for example, a glass sheet, a polyester film such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate film, as well as a polyamide film, a polycarbonate film, a polystyrene film, and a polyvinyl chloride resin film. These supports are suitably selected in accordance with the use and object of the photographic material.
- Exposure of the photographic material of the present invention for forming a photographic image thereon may be effected by any ordinary means.
- any one of various known light sources such as natural light (sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon-arc lamp, a carbon-arc lamp, a xenon-flash lamp, lasers, an LED and a CRT can be used for exposure.
- the exposing time may be any ordinary one for ordinary cameras of from 1/1000 second to one second.
- shorter exposures of less than 1/1000 second, for example from 1/10 6 to 1/10 4 second, may be applied to the photographic material of the present invention by the use of a xenon-flash lamp; or longer exposures of more than one second may be applied thereto.
- a color filter may be used for exposure of the photographic material of the present invention for adjusting the spectral composition of the light to be applied thereto.
- Laser rays may be used for exposure of the material.
- the material may also be exposed with a light to be emitted from phosphors as excited with electron rays, X rays, ⁇ rays or ⁇ rays.
- a reaction vessel To a reaction vessel were added 1000 ml of water, 25 g of deionized ossein gelatin, 15 ml of a 50% aqueous solution of NH 4 NO 3 and 7.5 ml of a 25% aqueous solution of NH 3 . The temperature of the mixture was kept at 50° C. with vigorous stirring. To the mixture were added 750 ml of an aqueous solution of 1N silver nitrate and an aqueous solution of 1N potassium bromide over a period of 50 minutes while the silver potential was kept at +60 mV versus saturated calomel electrode during the reaction. The aqueous solution of 1N potassium bromide was added in an amount necessary for keeping the silver potential at 60 mV.
- the resulting silver bromide grains were cubic and had a side length of 0.76 ⁇ 0.06 ⁇ m.
- the temperature of the resulting emulsion was lowered.
- a copolymer of isobutene and monosodium maleate as a flocculating agent was added thereto, and the emulsion was washed with water and desalted by a precipitation method.
- 95 g of deionized ossein gelatin and 430 ml of water were added thereto.
- the pH of the emulsion was adjusted to 6.5, and the pAg was adjusted to 8.3 at 50° C.
- Sodium thiosulfate was added thereto at 40° C., and the emulsion was ripened at 55° C. for 45 minutes so as to provide the optimum sensitivity.
- the emulsion contained 0.74 mol of silver bromide per kg.
- Sensitizing dyes shown in Tables 2 and 3 below were added to 55 g of the emulsion at 35° C., and the emulsion was ripened at 55° C. for 30 minutes. The temperature of the emulsion was lowered to 40° C., and the metallocene compounds shown in Tables 2 and 3 were added thereto. Further, 10 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 15 g of a 10% gel of deionized gelatin and 55 ml of water were added thereto. The resulting coating solution was coated on a cellulose triacetate film base in such an amount as to provide the following coating weights.
- the amount of the coating solution was set so as to provide 2.5 g/m 2 of silver and 3.8 g/m 2 of gelatin.
- An aqueous solution comprising mainly 0.22 g of sodium dodecylbenzenesulfonate per liter, 0.50 g of p-sulfostyrene sodium homopolymer per liter, 3.9 g of 1,3-bis-(vinylsulfonyl)-2-propanol per liter and 50 g of gelatin per liter was simultaneously coated as the upper layer in such an amount as to provide 1.0 g/m 2 of gelatin.
- Each of the coated samples prepared above was exposed to light through a continuous wedge for one second by using a tungsten lamp (2856° K.), a blue color filter V40 (a band pass filter which transmits light in the range of 370 to 440 nm, a product of Toshiba Glass Co., Ltd.) and an orange color filter SC 54 (which transmits light having a wavelength of 520 nm more, a product of Fuji Photo Film Co., Ltd.).
- a developing solution prepared by three times diluting D-72 developing solution and then adjusting the pH thereof to 10.4
- the density of each sample was measured by using a densitometer (a product of Fuji Photo Film Co., Ltd.) to determine the blue filter sensitivity (S B ), the orange filter sensitivity (S O ) and fog.
- the reciprocal of an exposure amount providing an optical density of (fog+0.2) is referred to as the sensitivity.
- the sensitivity in terms of the relative sensitivity is shown in Tables when each of the blue filter sensitivity and the orange filter sensitivity of each sample containing no metallocene compound in each group of the samples containing the same spectral sensitizing dye is referred to as 100.
- the silver halide emulsion used in Example 2 was prepared in the following manner.
- Solution (1) was heated to 50° C., and 262 ml of Solution (2) and 262 ml of Solution (3) were simultaneously added thereto at a given flow rate over a period of 12 minutes. Subsequently, Solution (4) and Solution (5) were simultaneously added thereto over a period of 20 minutes. The temperature of the mixture was lowered, and a copolymer of isobutene and monosodium maleate as a flocculating agent was added thereto, and the resulting emulsion was washed with water and desalted by a precipitation method. Water and ossein gelatin were then added thereto. The pH of the emulsion was adjusted to 6.1, and the pAg thereof was adjusted to 7.5.
- the thus prepared silver chlorobromide emulsion comprised monodisperse cubic grains having an average side length of 0.28 ⁇ m, a coefficient of variation (a value s/d obtained by dividing standard deviation by average side length) of 0.08 and a silver bromide content of 30 mol %.
- Sodium thiosulfate, chloroauric acid and potassium thiocyanate were added to the emulsion.
- the emulsion was ripened at 55° C. to carry out chemical sensitization so as to obtain the optimum sensitivity.
- the emulsion was divided into portions.
- the sensitizing dyes shown in Table 4 below were added to these portions at 50° C. as shown in Table 4 below.
- the metallocene compounds according to the present invention and 7.5 ⁇ 10 -4 mol of 4-hydroxy-5,6-propanol-1,3,3a,7-tetrazaindene per mol of silver chlorobromide were added as shown in Table 4 below.
- the emulsion was washed with water and desalted by a precipitation method. Subsequently, gelatin, water and phenol were added thereto. The pH of the emulsion was adjusted to 6.8, and the pAg thereof was adjusted to 8.7. The thus obtained silver halide grains had an average diameter of 1.74 ⁇ m and an average thickness of 0.23 ⁇ m (an average ratio of the diameter/the thickness was 7.57).
- the emulsion was divided into portions.
- the sensitizing dye shown in Table 5 below was added to each portion at 35° C. After the emulsion was ripened with stirring for 15 minutes, sodium thiosulfate pentahydrate, potassium tetraaurate and potassium thiocyanate were added thereto. The temperature was rapidly raised to 60° C., and the emulsion was ripened so as to obtain the optimum sensitivity.
- the metallocene compounds shown in Table 5 below were added to the thus prepared silver iodobromide emulsions at 40° C. Further, a 14% gel of deionized gelatin and 2 ⁇ 10 -3 mol of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mol of silver iodobromide were added thereto. After the mixture was mixed with stirring, each of the emulsions was coated on an antistatic-processed polyethylene terephthalate film base in the same manner as in Example 1.
- the coated samples were exposed to light and developed, and density was measured in the same manner as in Example 1.
- the results of the sensitivity and fog obtained are shown in Table 5 below.
- the reciprocal of an exposure amount providing an optical density of (fog+0.2) is referred to as the sensitivity.
- the sensitivity in terms of the relative sensitivity is shown in Table 5 below when each of the blue filter sensitivity (S B ) and the orange filter sensitivity (S O ) of each sample containing no metallocene compound in each group of the samples containing the same spectral sensitizing dyes is referred to as 100.
- Each layer had the following composition. Numerals represent coating weights (g/m 2 ). The amounts of the silver halide emulsions are represented by coating weights in terms of silver.
- all layer contained W-1, W-2, W-3, BP-4, BP-5, 5-methylthio-2-mercapto-1,3,4-thiadiazole, 1-p-carboxyphenyl-5-mercaptotetrazole, 1-m-sulfophenyl-5mercaptotetrazole, 5-nitro-1H-indazole, 5-methyl-1H-benzotriazole, 2-mercaptobenzothiazole, 6-(2-ethylhexanoylamino)-2-mercaptobenzimidazole, 1-m-(3-methylureido) phenyl-5-mercaptotetrazole, ⁇ -lipoic acid, 2-hydroxyamino-4,6-bis(hexylamino)-1,3,5-triazole, 2-hydroxyamino-4,6-bis(ethylamino)-1,3,5-triazole, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, sodium p-tol
- Sample 4-2 was prepared in the same manner as the preparation of Sample 4-1 except that 8.0 ⁇ 10 -3 mol of Metallocene Compound (I-1) according to the present invention was added to the first red-sensitive emulsion layer, 6.0 ⁇ 10 -3 mol of Metallocene Compound (I-1) was added to the second red-sensitive emulsion layer, and 7.5 ⁇ 10 -3 mol of Metallocene Compound (I-1) was added to the third red-sensitive emulsion layer before the coating of the emulsion, each amount being per mol of silver halide.
- Sample 4-3 was prepared in the same manner as in the preparation of Sample 4-2 except that an equal amount of Metallocene Compound (I-23) was used in place of Metallocene Compound (I-1).
- Sample 4-4 was prepared in the same manner as in the preparation of Sample 4-2 except that an equal amount of Metallocene Compound (I-26) was used in place of Metallocene Compound (I-1).
- Sample 4-5 was prepared in the same manner as in the preparation of Sample 4-2 except that Metallocene Compound (I-32) was used in place of Metallocene Compound (I-1).
- the processing solutions had the following compositions.
- Example 4 After the coated Samples 4-1, 4-2, 4-3 and 4-4 prepared in Example 4 were left to stand at room temperature for one year, the samples were exposed to light and developed in the same manner as in Example 4. The red filter sensitivity and fog were determined. The results obtained are shown in Table 8 below.
- the sensitivity in terms of the relative sensitivity is shown in Table 8 when the sensitivity of the corresponding sample stored in a refrigerator at -30° C. in an argon atmosphere during the corresponding period is referred to as 100.
- An increase or decrease in fog is also shown in comparison with the corresponding sample stored in a refrigerator at -30° C. in an argon atmosphere.
- the metallocene compounds according to the present invention are useful compounds for increasing sensitivity.
Abstract
Description
______________________________________ ##STR2## Compound No. V.sub.1 ______________________________________ (I-1) H (I-2) CO.sub.2 H (I-3) (CH.sub.2).sub.11 N.sup.⊕ (CH.sub.3).sub.3 I.sup.⊖ (I-4) CHO (I-5) SO.sub.3 H (I-6) ##STR3## (I-7) ##STR4## (I-8) B(OH).sub.2 (I-9) (CH.sub.2)N.sup.⊕ (CH.sub.3).sub.3 I.sup.⊖ (I-10) CH.sub.2 N(CH.sub.3).sub.2 (I-11) CO(CH.sub.2).sub.2 CO.sub.2 H (I-12) COCH.sub.3 (I-13) ##STR5## (I-14) CONH(CH.sub.2).sub.3 CH.sub.3 (I-15) CH.sub.2 OH (I-16) Cl (I-17) ##STR6## (I-18) CO(CH.sub.2).sub. 3 Br (I-19) CO(CH.sub.2).sub.3 OH (I-20) CO(CH.sub.2).sub.2 OH (I-21) CHNOH (I-22) CHN.sup.⊕O.sup.⊖ (I-23) CH.sub.2 SO.sub.3.sup.⊖ Na.sup.⊕ (I-24) CH.sub.2 OCH.sub.3 (I-25) CH.sub.2 NHCOCH.sub.3 (I-26) C.sub.2 H.sub.5 (I-27) CH(OH)CH.sub.3 (I-28) C(OH)(CH.sub.3).sub.2 (I-29) (CH.sub.2).sub.4 OH (I-30) CH(OH)(CH.sub.2).sub.2 CH.sub.2 OH (I-31) ##STR7## (I-32) ##STR8## (I-33) ##STR9## (I-34) ##STR10## (I-35) ##STR11## (I-36) and (I-37) ##STR12## (I-36) R = H (I-37) ##STR13## (I-38) ##STR14## (I-39) ##STR15## (I-40) ##STR16## (I-41) ##STR17## (I-42) ##STR18## (I-43) ##STR19## (I-44) ##STR20## (I-45) ##STR21## (I-46) ##STR22## (I-47) ##STR23## (I-48) ##STR24## (I-49) ##STR25## (I-50) ##STR26## (I-51) ##STR27## (I-52) ##STR28## ______________________________________
TABLE 1 ______________________________________ Additive RD 17643 RD18716 ______________________________________ 1 Chemical Sensitizing page 23 right column Agent of page 648 2 Sensitivity Increaser -- right column of page 648 3 Spectral Sensitizing pages 23-24 right column Agent, Supersensitizing of page 648 to Agent right column of page 649 4 Brightener page 24 5 Anti-fogging Agent, pages 24-25 right column Stabilizer of page 649 6 Light Absorber, Filter pages 25-26 right column Dye, UV Absorber of page 649 to left column of page 650 7 Anti-staining Agent right column left column to of page 25 right column of page 650 8 Dye Image Stabilizer page 25 9 Hardening Agent page 26 left column of page 651 10 Binder page 26 left column of page 651 11 Plasticizer, Lubricant page 27 right column of page 650 12 Coating Aid, Surfactant pages 26-27 right column of page 650 13 Antistatic Agent page 27 right column of page 650 ______________________________________
TABLE 2 __________________________________________________________________________ Sensitizing Dye Metallocene Compound Sample and Amount Added and Amount Added Relative Sensitivity No. (10.sup.-4 mol/molAg) (10.sup.-3 mol/molAg) S.sub.B S.sub.O Fog Remarks __________________________________________________________________________ 1-1 XII-1 1.5 -- -- 100 (standard) 100 (standard) 0.03 1-2 " " I-1 3.0 100 105 0.03 Invention 1-3 " " " 15.0 110 112 0.03 Invention 1-4 " " I-26 3.0 100 110 0.03 Invention 1-5 " " " 15.0 105 117 0.02 Invention 1-6 XII-19 2.5 -- -- 100 (standard) 100 (standard) 0.04 1-7 " " I-27 4.5 112 145 0.04 Invention 1-8 " " " 15.0 120 155 0.03 Invention 1-9 " " I-31 2.0 115 151 0.04 Invention 1-10 " " " 10.0 117 166 0.04 Invention 1-11 XIV-5 3.0 -- -- 100 (standard) 100 (standard) 0.03 1-12 " " I-1 3.0 105 123 0.04 Invention 1-13 " " " 15.0 112 174 0.03 Invention 1-14 " " I-23 3.0 123 132 0.04 Invention 1-15 " " " 15.0 120 234 0.03 Invention 1-16 XIVI-7 3.0 -- -- 100 (standard) 100 (standard) 0.03 1-17 " " I-1 3.0 105 126 0.03 Invention 1-18 " " " 15.0 120 195 0.03 Invention 1-19 " " I-2 0.3 123 155 0.03 Invention I-20 " " " 3.0 135 295 0.03 Invention 1-21 " " " 15.0 87 186 0.03 Invention 1-22 " " I-5 3.0 126 195 0.03 Invention 1-23 " " " 15.0 120 251 0.02 Invention 1-24 " " I-12 0.03 120 195 0.03 Invention 1-25 " " " 0.3 123 282 0.03 Invention 1-26 " " " 3.0 71 117 0.03 Invention 1-27 " " I-14 0.03 93 126 0.03 Invention 1-28 " " " 0.3 129 209 0.03 Invention 1-29 " " " 3.0 110 166 0.03 Invention __________________________________________________________________________
TABLE 3 __________________________________________________________________________ Sensitizing Dye Metallocene Compound Sample and Amount Added and Amount Added Relative Sensitivity No. (10.sup.-4 mol/molAg) (10.sup.-3 mol/molAg) S.sub.B S.sub.O Fog Remarks __________________________________________________________________________ 1-16 XIV-7 3.0 -- -- 100 (standard) 100 (standard) 0.03 1-30 " " I-15 0.03 145 195 0.03 Invention 1-31 " " " 0.3 110 331 0.03 Invention 1-32 " " " 15.0 110 112 0.03 Invention 1-33 " " I-31 0.3 107 129 0.03 Invention 1-34 " " " 3.0 117 162 0.02 Invention 1-35 " " " 15.0 138 240 0.03 Invention 1-36 XIV-7 4.5 -- -- 100 (standard) 100 (standard) 0.03 1-37 " " I-1 4.5 105 224 0.03 Invention 1-38 " " " 22.5 102 331 0.03 Invention 1-39 " " I-27 4.5 107 245 0.03 Invention 1-40 " " " 22.5 105 371 0.03 Invention 1-41 XII-8 3.0 -- -- 100 (standard) 100 (standard) 0.04 1-42 " " I-1 0.3 100 117 0.03 Invention 1-43 " " " 3.0 95 117 0.04 Invention 1-44 " " I-7 0.3 100 178 0.04 Invention 1-45 " " " 3.0 95 174 0.04 Invention 1-46 " " I-24 0.6 100 162 0.03 Invention __________________________________________________________________________
______________________________________ Solution (1) Water 1000 ml NaCl 4.65 g Gelatin 22 g Citric Acid 0.80 g Solution (2) KBr 25.3 g NaCl 32.3 g K.sub.2 IrCl.sub.6 (0.005%) 11.2 ml Na.sub.3 RhCl.sub.6.2H.sub.2 O (10.sup.-5 mol/liter) 18.9 ml Add Water to make 348 ml Solution (3) AgNO.sub.3 120.6 g Add Water to make 348 ml Solution (4) KBr 30.0 g NaCl 48.7 g Add Water to make 552 ml Solution (5) AgNO.sub.3 176.3 g Add Water to make 552 ml ______________________________________
TABLE 4 __________________________________________________________________________ Raw Pre- Sensitizing Dye Metallocene Compound servability Sample and Amount Added and Amount Added Relative Sensitivity with Time No. (10.sup.-4 mol/molAg) (10.sup.-3 mol/molAg) S.sub.B S.sub.O Fog ΔS.sub.O Remarks __________________________________________________________________________ 2-1 XI-5 8.0 -- -- 100 (standard) 100 (standard) 0.02 85 2-2 " " I-1 2.6 120 123 0.02 93 Invention 2-3 " " " 13.0 129 141 0.02 95 Invention 2-4 XI-14 2.5 -- -- 100 (standard) 100 (standard) 0.02 91 2-5 " " I-23 5.2 169 214 0.02 95 Invention 2-6 " " " 20.8 191 309 0.02 100 Invention 2-7 XI-16 2.5 -- -- 100 (standard) 100 (standard) 0.02 91 2-8 " " I-26 2.6 148 269 0.02 98 Invention 2-9 " " " 13.0 162 302 0.02 100 Invention 2-10 XI-40 5.0 -- -- 100 (standard) 100 (standard) 0.02 69 2-11 " " I-1 2.6 114 123 0.02 87 Invention 2-12 " " " 13.0 117 126 0.02 91 Invention 2-13 " " I-31 2.6 135 138 0.02 89 Invention 2-14 " " " 13.0 132 148 0.02 95 Invention 2-15 XI-44 6.8 -- -- 100 (standard) 100 (standard) 0.02 74 2-16 " " I-1 2.6 125 125 0.02 89 Invention 2-17 " " " 13.0 125 120 0.02 93 Invention 2-16 " " I-7 2.6 132 129 0.02 87 Invention 2-17 " " " 13.0 123 132 0.02 87 Invention 2-18 " " I-31 2.6 135 145 0.02 89 Invention 2-19 " " " 13.0 135 155 0.02 95 Invention 2-20 XIII-1 1.0 -- -- 100 (standard) 100 (standard) 0.02 89 2-21 " " II-31 0.1 115 120 0.02 89 Invention 2-22 " " " 1.0 135 162 0.02 93 Invention 2-23 " " " 10.0 129 209 0.02 95 Invention __________________________________________________________________________
TABLE 5 __________________________________________________________________________ Sensitizing Dye Metallocene Compound Latent Image Sample and Amount Added and Amount Added Relative Sensitivity Stability No. (10.sup.-4 mol/molAg) (10.sup.-3 mol/molAg) S.sub.B S.sub.O Fog ΔS.sub.O Remarks __________________________________________________________________________ 3-1 XI-35 7.1 -- -- 100 (standard) 100 (standard) 0.03 87 3-2 " " I-1 0.3 100 123 0.03 93 Invention 3-3 " " " 3.0 100 117 0.03 98 Invention 3-4 " " I-13 0.3 100 145 0.03 91 Invention 3-5 " " " 3.0 100 162 0.03 98 Invention 3-6 " " " 15.0 95 148 0.03 102 Invention 3-7 XIV-3 4.7 -- -- 100 (standard) 100 (standard) 0.03 91 3-8 " " I-26 2.6 148 269 0.03 98 Invention 3-9 " " " 13.0 162 302 0.03 100 Invention 3-10 XIV-7 4.7 -- -- 100 (standard) 100 (standard) 0.03 89 3-11 " " I-1 3.0 100 115 0.03 95 Invention 3-12 " " " 15.0 105 134 0.03 98 Invention 3-13 " " I-23 0.6 100 138 0.03 91 Invention 3-14 " " " 3.0 115 155 0.03 95 Invention 3-15 " " " 15.0 120 170 0.03 95 Invention 3-16 " " I-32 0.6 100 120 0.03 93 Invention 3-17 " " " 3.0 110 138 0.03 100 Invention 3-18 " " " 10.0 95 132 0.04 100 Invention __________________________________________________________________________
______________________________________ First Layer (antihalation layer) Black Colloidal Silver 0.18 (in terms of silver) Gelatin 1.40 Second Layer (interlayer) 2,5-Di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third Layer (first red-sensitive emulsion layer) Emulsion A (in terms of silver) 0.25 Emulsion B (in terms of silver) 0.25 Sensitizing Dye (XI-1) 6.9 × 10.sup.-5 Sensitizing Dye (XIV-15) 1.8 × 10.sup.-5 Sensitizing Dye (XIV-7) 3.1 × 10.sup.-5 EX-2 0.34 EX-10 0.02 U-1 0.07 U-2 0.05 U-3 0.07 HBS-1 0.06 Gelatin 0.87 Fourth Layer (second red-sensitive emulsion layer) Emulsion G (in terms of silver) 1.00 Sensitizing Dye (XI-1) 5.1 × 10.sup.-5 Sensitizing Dye (XIV-15) 1.4 × 10.sup.-5 Sensitizing Dye (XIV-7) 2.3 × 10.sup.-5 EX-2 0.40 EX-3 0.05 EX-10 0.015 U-1 0.07 U-2 0.05 U-3 0.07 Gelatin 1.30 Fifth Layer (third red-sensitive emulsion layer) Emulsion D (in terms of silver) 1.60 Sensitizing Dye (XI-1) 5.4 × 10.sup.-5 Sensitizing Dye (XIV-15) 1.4 × 10.sup.-5 Sensitizing Dye (XIV-7) 2.4 × 10.sup.-5 EX-2 0.097 EX-3 0.01 EX-4 0.08 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 Sixth Layer (interlayer) EX-5 0.04 HBS-1 0.02 Gelatin 0.80 Seventh Layer (first green-sensitive emulsion layer) Emulsion A (in terms of silver) 0.15 Emulsion B (in terms of silver) 0.15 Sensitizing Dye (XI-45) 3.0 × 10.sup.-5 Sensitizing Dye (XI-48) 1.0 × 10.sup.-4 Sensitizing Dye (XI-38) 3.8 × 10.sup.-4 EX-1 0.021 EX-6 0.26 EX-7 0.03 EX-8 0.025 HBS-1 0.10 HBS-3 0.01 Gelatin 0.63 Eighth Layer (second green-sensitive emulsion layer) Emulsion C (in terms of silver) 0.45 Sensitizing Dye (XI-45) 2.1 × 10.sup.-5 Sensitizing Dye (XI-48) 7.0 × 10.sup.-5 Sensitizing Dye (XI-38) 2.6 × 10.sup.-4 EX-6 0.094 EX-7 0.026 EX-8 0.018 HBS-1 0.16 HBS-3 0.008 Gelatin 0.50 Ninth Layer (third green-sensitive emulsion layer) Emulsion E (in terms of silver) 1.20 Sensitizing Dye (XI-45) 3.5 × 10.sup.-5 Sensitizing Dye (XI-48) 8.0 × 10.sup.-5 Sensitizing Dye (XI-38) 3.0 × 10.sup.-4 EX-1 0.025 EX-11 0.10 EX-13 0.015 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 Tenth Layer (yellow filter layer) Yellow Colloidal Silver 0.05 (in terms of silver) EX-5 0.08 HBS-1 0.03 Gelatin 0.95 Eleventh Layer (first blue-sensitive emulsion layer) Emulsion A (in terms of silver) 0.08 Emulsion B (in terms of silver) 0.07 Emulsion F (in terms of silver) 0.07 Sensitizing Dye (XI-28) 3.5 × 10.sup.-4 EX-8 0.042 EX-9 0.72 HBS-1 0.28 Gelatin 1.10 Twelfth Layer (second blue-sensitive emulsion layer) Emulsion G (in terms of silver) 0.45 Sensitizing Dye (XI-28) 2.1 × 10.sup.-4 EX-9 0.15 EX-10 0.007 HBS-1 0.05 Gelatin 0.78 Thirteenth Layer (third blue-sensitive emulsion layer) Emulsion H (in terms of silver) 0.77 Sensitizing Dye (XI-28) 2.2 × 10.sup.-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 Fourteenth Layer (first protective layer) Emulsion I (in terms of silver) 0.20 U-4 0.11 U-5 0.17 HBS-1 0.05 Gelatin 1.00 Fifteenth Layer (second protective layer) HA-1 0.40 BP-1 (diameter: 1.7 μm) 0.05 BP-2 (diameter: 1.7 μm) 0.10 BP-3 0.10 S-1 0.20 Gelatin 1.20 ______________________________________
TABLE 6 __________________________________________________________________________ Coefficient Average Mean of Variation AgI Grain in Grain Size Ratio of Content Size Distribution Diameter/ Emulsion (%) (μm) (%) Thickness Ratio of Amount of Silver (AgI content __________________________________________________________________________ %) A 4.0 0.45 27 1 core/shell = 1/3(13/1), double structural grains B 8.9 0.70 14 1 core/shell = 3/7(25/2), double structural grains C 10 0.75 30 2 core/shell = 1/2(24/3), double structural grains D 16 1.05 35 2 core/shell = 4/6(40/0), double structural grains E 10 1.05 35 3 core/shell = 1/2(24/3), double structural grains F 4.0 0.25 28 1 core/shell = 1/3(13/1), double structural grains G 14.0 0.75 25 2 core/shell = 1/2(42/0), double structural grains H 14.5 1.30 25 3 core/shell = 37/63(34/3), double structural grains I 1 0.07 15 1 uniform structural grains __________________________________________________________________________ ##STR40##
______________________________________ Process- ing Processing Temper- Tank Stage Time ature Replenisher Capacity ______________________________________ Color 2 min 45 sec 38° C. 33 ml 20 liters Develop- ment Bleaching 6 min 30 sec 38° C. 25 ml 40 liters Rinsing 2 min 10 sec 24° C. 1200 ml 20 liters Fixing 4 min 20 sec 38° C. 25 ml 30 liters Rinsing (1) 1 min 05 sec 24° C. counter-current 10 liters system of from (2) to (1) Rinsing (2) 1 min 00 sec 24° C. 1200 ml 10 liters Stabiliza- 1 min 05 sec 38° C. 25 ml 10 liters tion Drying 4 min 20 sec 55° C. ______________________________________ Replenisher being per 1 m long by 35 mm wide
______________________________________ Mother Solution Replenisher (g) (g) ______________________________________ Color developing Solution Diethylenetriamine- 1.0 1.1 pentaacetic Acid 1-Hydroxyethylidene-1,1- 3.0 3.2 diphosphonic Acid Sodium Sulfite 4.0 4.4 Potassium Carbonate 30.0 37.0 Potassium Bromide 1.4 0.7 Potassium Iodide 1.5 mg -- Hydroxylamine Sulfate 2.4 2.8 4-[N-Ethyl-N-β-hydroxy- 4.5 5.5 ethylamino]-2-methylaniline Sulfate Add Water to make 1.0 liter 1.0 liter pH 10.05 10.10 Bleaching Solution Sodium Ethylenediamine- 100.0 120.0 tetraacetato Ferrate Trihydrate Disodium Ethylenediamine- 10.0 11.0 tetraacetate Ammonium Bromide 140.0 160.0 Ammonium Nitrate 30.0 35.0 Ammonia Water (27%) 6.5 ml 4.0 ml Add Water to make 1.0 liter 1.0 liter pH 6.0 5.7 Fixing Solution Disodium Ethylenediamine- 0.5 0.7 tetraacetate Sodium Sulfite 7.0 8.0 Sodium Bisulfite 5.0 5.5 Aqueous Solution of 170.0 ml 200.0 ml Ammonium Thiosulfate (70%) Add Water to make 1.0 liter 1.0 liter pH 6.7 6.6 Stabilizing Solution Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene p-Monononyl- 0.3 0.45 phenyl Ether (an average degree of polymerization: 10) Disodium Ethylenediamine- 0.05 0.08 tetraacetate Add Water to make 1.0 liter 1.0 liter pH 5.0 to 8.0 5.8 to 8.0 ______________________________________
TABLE 7 ______________________________________ Relative Red Increase or Sample Metallocene Sensitivity Decrease No. Compound S.sub.R in Fog Remarks ______________________________________ 4-1 -- 100 (standard) (standard) 4-2 I-1 112 -0.01 Invention 4-3 I-23 123 0.02 Invention 4-4 I-26 129 0.02 Invention 4-5 I-32 123 0.01 Invention ______________________________________
TABLE 8 ______________________________________ Relative Red Increase or Sample Metallocene Sensitivity Decrease No. Compound S.sub.R in Fog Remarks ______________________________________ 4-1 -- 87 -0.01 4-2 I-1 93 -0.01 Invention 4-3 I-23 98 0.02 Invention 4-4 I-26 100 0.02 Invention 4-5 I-32 95 0.01 Invention ______________________________________
Claims (9)
Applications Claiming Priority (2)
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JP5-169797 | 1993-06-17 | ||
JP05169797A JP3116097B2 (en) | 1993-06-17 | 1993-06-17 | Silver halide photographic material |
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US5457022A true US5457022A (en) | 1995-10-10 |
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Application Number | Title | Priority Date | Filing Date |
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US08/262,340 Expired - Lifetime US5457022A (en) | 1993-06-17 | 1994-06-17 | Silver halide photographic material |
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JP (1) | JP3116097B2 (en) |
Cited By (10)
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US5667958A (en) * | 1994-11-15 | 1997-09-16 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US5821044A (en) * | 1996-07-25 | 1998-10-13 | Agfa-Gevaert Aktiengesellschaft | Photographic silver halide emulsions |
US6054259A (en) * | 1997-03-18 | 2000-04-25 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US6498002B2 (en) | 2000-07-27 | 2002-12-24 | Agfa-Gevaert | Photographic silver halide material |
US20040038159A1 (en) * | 2001-09-26 | 2004-02-26 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US20050101059A1 (en) * | 2003-10-24 | 2005-05-12 | Xhp Microsystems, Inc. | Method and system for hermetically sealing packages for optics |
US20060046429A1 (en) * | 2004-08-30 | 2006-03-02 | Miradia Inc. | Laser based method and device for forming spacer structures for packaging optical reflection devices |
US20060121693A1 (en) * | 2004-12-08 | 2006-06-08 | Miradia Inc. | Method and device for wafer scale packaging of optical devices using a scribe and break process |
US7291449B2 (en) * | 1999-03-30 | 2007-11-06 | Fujifilm Corporation | Silver halide photographic material and methine dye |
US20080138957A1 (en) * | 2005-05-31 | 2008-06-12 | Miradia Inc. | Triple alignment substrate method and structure for packaging devices |
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GB0614338D0 (en) * | 2006-07-19 | 2006-08-30 | Acal Energy Ltd | Fuel cells |
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US4719174A (en) * | 1983-06-17 | 1988-01-12 | Fuji Photo Film Co., Ltd. | Direct positive silver halide photographic light-sensitive material depress formation of re-reversed negative image |
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US5667958A (en) * | 1994-11-15 | 1997-09-16 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US5821044A (en) * | 1996-07-25 | 1998-10-13 | Agfa-Gevaert Aktiengesellschaft | Photographic silver halide emulsions |
US6054259A (en) * | 1997-03-18 | 2000-04-25 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US7291449B2 (en) * | 1999-03-30 | 2007-11-06 | Fujifilm Corporation | Silver halide photographic material and methine dye |
US6498002B2 (en) | 2000-07-27 | 2002-12-24 | Agfa-Gevaert | Photographic silver halide material |
US7052827B2 (en) | 2001-09-26 | 2006-05-30 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US20040038159A1 (en) * | 2001-09-26 | 2004-02-26 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US6828087B2 (en) * | 2001-09-26 | 2004-12-07 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US20050037296A1 (en) * | 2001-09-26 | 2005-02-17 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US20070235852A1 (en) * | 2003-10-24 | 2007-10-11 | Miradia Inc. | Method and system for sealing packages for optics |
US7948000B2 (en) | 2003-10-24 | 2011-05-24 | Miradia Inc. | Method and system for hermetically sealing packages for optics |
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US20060284295A1 (en) * | 2003-10-24 | 2006-12-21 | Miradia Inc. | Method and system for hermetically sealing packages for optics |
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US7303645B2 (en) | 2003-10-24 | 2007-12-04 | Miradia Inc. | Method and system for hermetically sealing packages for optics |
US20080014682A1 (en) * | 2003-10-24 | 2008-01-17 | Miradia Inc. | Method and system for sealing packages for optics |
US20110186839A1 (en) * | 2003-10-24 | 2011-08-04 | Miradia Inc. | Method and System for Hermetically Sealing Packages for Optics |
US7671461B2 (en) | 2003-10-24 | 2010-03-02 | Miradia Inc. | Method and system for hermetically sealing packages for optics |
US20060046429A1 (en) * | 2004-08-30 | 2006-03-02 | Miradia Inc. | Laser based method and device for forming spacer structures for packaging optical reflection devices |
US7064045B2 (en) * | 2004-08-30 | 2006-06-20 | Miradia Inc. | Laser based method and device for forming spacer structures for packaging optical reflection devices |
US20080191221A1 (en) * | 2004-12-08 | 2008-08-14 | Miradia Inc. | Method and device for wafer scale packaging of optical devices using a scribe and break process |
US7825519B2 (en) | 2004-12-08 | 2010-11-02 | Miradia Inc. | Method and device for wafer scale packaging of optical devices using a scribe and break process |
US20110012166A1 (en) * | 2004-12-08 | 2011-01-20 | Miradia Inc. | Method and device for wafer scale packaging of optical devices using a scribe and break process |
US20060121693A1 (en) * | 2004-12-08 | 2006-06-08 | Miradia Inc. | Method and device for wafer scale packaging of optical devices using a scribe and break process |
US7344956B2 (en) | 2004-12-08 | 2008-03-18 | Miradia Inc. | Method and device for wafer scale packaging of optical devices using a scribe and break process |
US9006878B2 (en) | 2004-12-08 | 2015-04-14 | Miradia Inc. | Method and device for wafer scale packaging of optical devices using a scribe and break process |
US7542195B2 (en) | 2005-05-31 | 2009-06-02 | Miradia Inc. | Triple alignment substrate method and structure for packaging devices |
US20080138957A1 (en) * | 2005-05-31 | 2008-06-12 | Miradia Inc. | Triple alignment substrate method and structure for packaging devices |
Also Published As
Publication number | Publication date |
---|---|
JPH075615A (en) | 1995-01-10 |
JP3116097B2 (en) | 2000-12-11 |
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